Estimating the Adsorption Thermodynamics of a Toxic Pollutant by Activated Carbon Coated with Superparamagnetic Nanoparticles Using Isothermal Titration Calorimetry
Publication: Journal of Hazardous, Toxic, and Radioactive Waste
Volume 28, Issue 3
Abstract
In the present work, the thermodynamic parameters for the adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D), a herbicide, onto biomass-based activated carbon coated with magnetite nanoparticles (ACM) were estimated using a high-precision isothermal titration calorimeter (ITC). The obtained thermodynamic parameters, such as change in Gibb’s free energy (ΔG), change in enthalpy (ΔH), and change in entropy (ΔS), were compared with the values computed applying conventional methods using equilibrium isotherm model parameters. The thermodynamic parameters suggested that the adsorption of 2,4-D onto ACM was spontaneous and exothermic. ITC proved to be an efficient experimental method in determining the thermodynamic parameters for the adsorption process with minimal adsorbent, adsorbate, and time consumption. The application of ITC can also be extended to determine the thermodynamic parameters of various solid–liquid interactions involved in different processes.
Practical Applications
The 2,4-dichlorophenoxyacetic acid (2,4-D) is commonly used as a herbicide, and its occurrence is reported widely in aquatic bodies. Adsorption process using activated carbon impregnated with iron nanoparticles proved to be effective in removing these 2,4-D from the aquatic phase. In general, adsorption dynamics are demonstrated by isotherm, kinetics, and thermodynamic studies so that it can be extended to real-world applications. Conventionally, adsorption thermodynamic parameters are estimated from equilibrium isotherm constants. However, the determination of these parameters using the isotherm constants may not be accurate. Hence, sophisticated equipment such as isothermal titration calorimeter (ITC) can be used as an efficient tool to accurately compute the thermodynamic parameters in less time with minimal requirement of reagents.
Get full access to this article
View all available purchase options and get full access to this article.
Data Availability Statement
All the data, models, or code that support the findings of this study are available from the corresponding author upon reasonable request.
References
Ahire, S. A., A. A. Bachhav, T. B. Pawar, B. S. Jagdale, A. V. Patil, and P. B. Koli. 2022. “The augmentation of nanotechnology era: A concise review on fundamental concepts of nanotechnology and applications in material science and technology.” Results Chem. 4: 100633. https://doi.org/10.1016/j.rechem.2022.100633.
Al-Ghouti, M. A., and D. A. Daana. 2020. “Guidelines for the use and interpretation of adsorption isotherm models: A review.” J. Hazard. Mater. 393: 122383. https://doi.org/10.1016/j.jhazmat.2020.122383.
Binh, Q. A., and H.-H. Nguyen. 2020. “Investigation the isotherm and kinetics of adsorption mechanism of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) on corn cob biochar.” Bioresour. Technol. Rep. 11: 100520. https://doi.org/10.1016/j.biteb.2020.100520.
Cavalcanti, I. D. L., Jr. F. H. Xavier, N. S. S. Magalhaes, and M. C. B. L. Nogueira. 2023. “Isothermal titration calorimetry (ITC) as a promising tool in pharmaceutical nanotechnology.” Int. J. Pharm. 641: 123063. https://doi.org/10.1016/j.ijpharm.2023.123063.
Chang, P.-H., R. Mukhopadhyay, C.-Y. Chen, B. Sarkar, J. Li, and Y.-M. Tzou. 2023. “A mechanistic insight into the shrinkage and swelling of Ca-montmorillonite upon adsorption of chain-like ranitidine in an aqueous system.” J. Colloid Interface Sci. 633: 979–991. https://doi.org/10.1016/j.jcis.2022.11.104.
Daems, E., G. Moro, R. Campos, and K. De Wael. 2021. “Mapping the gaps in chemical analysis for the characterisation of aptamer-target interactions.” TrAC, Trends Anal. Chem. 142: 116311. https://doi.org/10.1016/j.trac.2021.116311.
Dargahi, A., K. Hasani, S. A. Mokhtari, M. Vosoughi, M. Moradi, and Y. Vaziri. 2021. “Highly effective degradation of 2,4-Dichlorophenoxyacetic acid herbicide in a three-dimensional sono-electro-Fenton (3D/SEF) system using powder activated carbon (PAC)/Fe3O4 as magnetic particle electrode.” J. Environ. Chem. Eng. 9: 105889. https://doi.org/10.1016/j.jece.2021.105889.
Ding, L., X. Lu, H. Deng, and X. Zhang. 2012. “Adsorptive removal of 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous solutions using MIEX resin.” Ind. Eng. Chem. Res. 51: 11226–11235. https://doi.org/10.1021/ie300469h.
Drout, R. J., S. Kato, H. Chen, F. A. Son, K.-i. Otake, T. Islamoglu, R. Q. Snurr, and O. K. Farha. 2020. “Isothermal titration calorimetry to explore the parameter space of organophosphorus agrochemical adsorption in MOFs.” J. Am. Chem. Soc. 142: 12357–12366. https://doi.org/10.1021/jacs.0c04668.
Gupta, V. K., I. Ali, Suhas, and V. K. Saini. 2006. “Adsorption of 2,4-D and carbofuran pesticides using fertilizer and steel industry wastes.” J. Colloid Interface Sci. 299: 556–563. https://doi.org/10.1016/j.jcis.2006.02.017.
Hameed, B. H., J. M. Salman, and A. L. Ahmad. 2009. “Adsorption isotherm and kinetic modeling of 2,4-D pesticide on activated carbon derived from date stones.” J. Hazard. Mater. 163: 121–126. https://doi.org/10.1016/j.jhazmat.2008.06.069.
Harrison, J. A., A. Pruska, I. Oganesyan, P. Bittner, and R. Zenobi. 2021. “Temperature-controlled electrospray ionization: Recent progress and applications.” Chem. Eur. J. 27 (72): 18015–18028. https://doi.org/10.1002/chem.202102474.
Jung, B. K., Z. Hasan, and S. H. Jhung. 2013. “Adsorptive removal of 2,4-dichlorophenoxyacetic acid (2,4-D) from water with a metal–organic framework.” Chem. Eng. J. 234: 99–105. https://doi.org/10.1016/j.cej.2013.08.110.
Kamaraj, R., D. J. Davidson, G. Sozhan, and S. Vasudevan. 2014. “Adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) from water by in situ generated metal hydroxides using sacrificial anodes.” J. Taiwan Inst. Chem. Eng. 45: 2943–2949. https://doi.org/10.1016/j.jtice.2014.08.006.
Kermani, M., F. Mohammadi, B. Kakavandi, A. Esrafili, and Z. Rostamifasih. 2018. “Simultaneous catalytic degradation of 2,4-D and MCPA herbicides using sulfate radical-based heterogeneous oxidation over persulfate activated by natural hematite (α-Fe2O3/PS).” J. Phys. Chem. Solids 117: 49–59. https://doi.org/10.1016/j.jpcs.2018.02.009.
Kontogeorgis, G. M., R. Dohrn, I. G. Economou, J.-C. de Hemptinne, A. ten Kate, D. Kuitunen, M. Mooijer, L. F. Zilnik, and V. Vesovic. 2021. “Industrial requirements for thermodynamic and transport properties: 2020.” Ind. Eng. Chem. Res. 60 (13): 4987–5013. https://doi.org/10.1021/acs.iecr.0c05356.
Lima, E. C., A. Hosseini-Bandegharaei, J. C. Moreno-Pirajan, and I. Anastopoulos. 2019. “A critical review of the estimation of the thermodynamic parameters on adsorption equilibria. Wrong use of equilibrium constant in the Van’t Hoof equation for calculation of thermodynamic parameters of adsorption.” J. Mol. Liq. 273: 425–434. https://doi.org/10.1016/j.molliq.2018.10.048.
Liu, W., Q. Yang, Z. Yang, and W. Wang. 2016a. “Adsorption of 2,4-D on magnetic graphene and mechanism study.” Colloids Surf., A 509: 367–375. https://doi.org/10.1016/j.colsurfa.2016.09.039.
Liu, Y. 2009. “Is the free energy change of adsorption correctly calculated?” J. Chem. Eng. Data 54: 1981–1985. https://doi.org/10.1021/je800661q.
Liu, Y., C. N. Ong, and J. Xie. 2016b. “Emerging nanotechnology for environmental applications.” Nanotechnol. Rev. 5: 1–2. https://doi.org/10.1515/ntrev-2015-0072.
Moreno-Pirajan, J. C., and L. Giraldo. 2012. “Design, construction, and calibration of an isothermal titration calorimeter and its application in the study of the adsorption of phenolic compounds.” Rev. Sci. Instrum. 83: 015117. https://doi.org/10.1063/1.3680596.
Munusamy, S., R. Conde, B. Bertrand, and C. Munoz-Garay. 2020. “Biophysical approaches for exploring lipopeptide-lipid interactions.” Biochimie 170: 173–202. https://doi.org/10.1016/j.biochi.2020.01.009.
Nejati, K., S. Davary, and M. Saati. 2013. “Study of 2,4-dichlorophenoxyacetic acid (2,4-D) removal by Cu-Fe-layered double hydroxide from aqueous solution.” Appl. Surf. Sci. 280: 67–73. https://doi.org/10.1016/j.apsusc.2013.04.086.
Nethaji, S., A. Sivasamy, and A. B. Mandal. 2013. “Preparation and characterization of corn cob activated carbon coated with nano-sized magnetite particles for the removal of Cr(VI).” Bioresour. Technol. 134: 94–100. https://doi.org/10.1016/j.biortech.2013.02.012.
Ortega, P. F. R., J. P. C. Trigueiro, M. R. Santos, Â. M. L. Denadai, L. C. A. Oliveira, A. P. C. Teixeira, G. G. Silva, and R. L. Lavall. 2017. “Thermodynamic study of methylene blue adsorption on carbon nanotubes using isothermal titration calorimetry: A simple and rigorous approach.” J. Chem. Eng. Data 62 (2): 729–737. https://doi.org/10.1021/acs.jced.6b00804.
Pan, Y., S. Zhou, and J. Guan. 2020. “Computationally identifying hot spots in protein-DNA binding interfaces using an ensemble approach.” BMC Bioinf. 21: 384. https://doi.org/10.1186/s12859-020-03675-3.
Pierce, M. M., C. S. Raman, and B. T. Nall. 1999. “Isothermal titration calorimetry of protein-protein interactions.” Methods 19: 213–221. https://doi.org/10.1006/meth.1999.0852.
Prado, A. G. S., A. O. Moura, R. D. A. Andrade, I. C. Pescara, V. S. Ferreira, E. A. Faria, A. H. A. de Oliveira, E. Y. A. Okino and L. F. Zara. 2010. “Application of Brazilian sawdust samples for chromium removal from tannery wastewater.” J. Therm. Anal. Calorim. 99: 681–687. https://doi.org/10.1007/s10973-009-0284-0.
Pradhan, D., L. B. Sukla, B. B. Mishra, and N. Devi. 2019. “Biosorption for removal of hexavalent chromium using microalgae Scenedesmus sp.” J. Cleaner Prod. 209: 617–629. https://doi.org/10.1016/j.jclepro.2018.10.288.
Ramesh, A., D. J. Lee, and J. W. C. Wong. 2005. “Thermodynamic parameters for adsorption equilibrium of heavy metals and dyes from wastewater with low-cost adsorbents.” J. Colloid Interface Sci. 291: 588–592. https://doi.org/10.1016/j.jcis.2005.04.084.
Samarghandi, M. R., D. Nemattollahi, G. Asgari, R. Shokoohi, A. Ansari, and A. Dargahi. 2019. “Electrochemical process for 2,4-D herbicide removal from aqueous solutions using stainless steel 316 and graphite Anodes: Optimization using response surface methodology.” Sep. Sci. Technol. 54: 478–493. https://doi.org/10.1080/01496395.2018.1512618.
Shval, A., and Y. Mastai. 2011. “Isothermal titration calorimetry as a new tool to investigate chiral interactions at crystal surfaces.” Chem. Commun. 47: 5735–5737. https://doi.org/10.1039/C0CC05403H.
Srivastava, V. C., I. D. Mall, and I. M. Mishra. 2007. “Adsorption thermodynamics and isosteric heat of adsorption of toxic metal ions onto bagasse fly ash (BFA) and rice husk ash (RHA).” Chem. Eng. J. 132 (2): 267–278. https://doi.org/10.1016/j.cej.2007.01.007.
Tan, I. A. W., A. L. Ahmad, and B. H. Hameed. 2009. “Adsorption isotherms, kinetics, thermodynamics and desorption studies of 2,4,6-trichlorophenol on oil palm empty fruit bunch-based activated carbon.” J. Hazard. Mater. 164: 473–482. https://doi.org/10.1016/j.jhazmat.2008.08.025.
Tran, H. N., Y.-F. Wang, S.-J. You, and H.-P. Chao. 2017. “Insights into the mechanism of cationic dye adsorption on activated charcoal: The importance of π–π interactions.” Process Saf. Environ. Prot. 107: 168–180. https://doi.org/10.1016/j.psep.2017.02.010.
Trivedi, N. S., R. A. Kharkar, and S. A. Mandavgane. 2019. “Use of wheat straw combustion residues for removal of chlorinated herbicide (2,4-dichlorophenoxyacetic acid).” Waste Biomass Valorization 10: 1323–1331. https://doi.org/10.1007/s12649-017-0134-4.
Varsha, M., P. S. Kumar, and B. S. Rathi. 2022. “A review on recent trends in the removal of emerging contaminants from aquatic environment using low-cost adsorbents.” Chemosphere 287 (3): 132270. https://doi.org/10.1016/j.chemosphere.2021.132270.
Wang, L., W. Zhang, Y. Shao, D. Zhang, G. Guo, and X. Wang. 2022. “Analytical methods for obtaining binding parameters of drug–protein interactions: A review.” Anal. Chim. Acta 1219: 340012. https://doi.org/10.1016/j.aca.2022.340012.
Wu, D., and P. Grzegorz. 2020. “Measuring the affinity of protein-protein interactions on a single-molecule level by mass photometry.” Anal. Biochem. 592: 113575. https://doi.org/10.1016/j.ab.2020.113575.
Yagmur, H. K., and I. Kaya. 2021. “Synthesis and characterization of magnetic ZnCl2-activated carbon produced from coconut shell for the adsorption of methylene blue.” J. Mol. Struct. 1232: 130071. https://doi.org/10.1016/j.molstruc.2021.130071.
Zhang, W., J. Song, Q. He, H. Wang, W. Lyu, H. Feng, W. Xiong, W. Guo, J. Wu, and L. Chen. 2020. “Novel pectin based composite hydrogel derived from grapefruit peel for enhanced Cu(II) removal.” J. Hazard. Mater. 384: 121445. https://doi.org/10.1016/j.jhazmat.2019.121445.
Information & Authors
Information
Published In
Journal of Hazardous, Toxic, and Radioactive Waste
Volume 28 • Issue 3 • July 2024
Copyright
© 2024 American Society of Civil Engineers.
History
Received: Jul 14, 2023
Accepted: Dec 18, 2023
Published online: Feb 21, 2024
Published in print: Jul 1, 2024
Discussion open until: Jul 21, 2024
ASCE Technical Topics:
- Activated carbon
- Adsorption
- Carbon
- Chemical compounds
- Chemical elements
- Chemical processes
- Chemicals
- Chemistry
- Continuum mechanics
- Dynamics (solid mechanics)
- Engineering fundamentals
- Engineering materials (by type)
- Engineering mechanics
- Environmental engineering
- Forces (type)
- Magnetic fields
- Material mechanics
- Materials engineering
- Mathematics
- Nanomechanics
- Parameters (statistics)
- Particles
- Solid mechanics
- Sorption
- Statistics
- Thermal effects
- Thermodynamics
Authors
Metrics & Citations
Metrics
Citations
Download citation
If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.